Red monazo wool dyes



Patented Apr. 17, 1945 RED MONAZO Y WOOL DYES Donovan E. Kvalnes, Penns Grove, N. J., assignor to E. I. du Pont de 'Nemours & Company, Wilmington, DeL, a corporation of Delaware No Drawing. Application April 18, 1942,

- Serial No. 439,558

GClaims. (01.fate -1'991' r This invention relates to red monazo wool dyes, and especially to a class of such monazo dyes in which the coupling component is 2-amino-8- naphthol-G-sulfonic acid, thecoupling is ortho toamino and the diazo component has a chloroor bromo-acylamino side chain which is meta or para to the diazo group.

represented in general by. the formula .n-cHx-co-HN 7 I I N=N son; H

andicouplir'ig acid medium with Z-amino- BOIH wherein X is chlorine or bromine, R is hydrogen or methyl and the group'R-CHX-CO-HN- is meta or para to the azo group.

Dyes have been made heretofore which are similar in constitution to those of the present 7 cni-co-umor CsHsCONH. The. dyes of the present inven- I .tion have a surprising fastness to perspiration,

invention exceptthat the group corresponding to theR--CHXCONH- group is been accounted for; by thedifference in the side chain of the diazo component.

' It is among the objects of the present invention to provide new fast-to-light red wool dyesvwhi'ch are further characterized by good fastness to washing, iulling and perspiration. Other objects of the'invention will be apparent from the 1'01- lowing description.

The objects of the invention may be attained by treatment of the known dyes NE:

SOaH

qwith an acid halide oranhydride of acids of the The invention-will be more fully setforth in the following more detailed description which includes examples that aregiven as illustrative embodiments of the, invention and not as limitav v tions,'thereofiflflParts are expressed in parts by The compounds oi! the present invention are weight votliei wisia notedi Example 1 A solutionof 265 parts ,of 2-s ulfo-4-chloro- Z acetylamino aniline in 1500 parts of water and 40 parts of. sodium hydroxide are cooled to 0 C. by the addition ofice. Then 110 parts of hydrogen chloride (as a 22% solution) are added, immediately followed by 69 partspf sodium nitrite. (asa 30% 'so1uti'on). The temperature is maintained at 0+5 0. until diazotization is complete. The excess nitrous acid is destroyed by theadditio'n .of a'small amount of sulfamic acid.

A, clear solution, of 250 parts of 2-amino-8- naphtholgfi jsulfonicacid in 800 parts of water and 4 1.5 parts of sodium hydroxide, made slightly acid to blue litmus paper, is cooled to 10 C. by thefjadditionpof ice. The above diazo solution is added rapidly, and a solution of sodium acetate is added graduallyuntil the coupling mixture is no longer acid to Congo red paper. When coupling is complete, the mixture is rendered alkaline to Brilliant Yellow paper by the addition of sodium hydroxide solution, and 10% salt by volume is added. Thedye is isolated'by filtration and I dried at 40-50 0.1 The compound is represented by the formula ClCHaCO-NH-QN=N- y I 03B 119 4 SQsH It dyes wool from an acid'batli (for'instance 3% suliuricon' the weight of the wool used) a pleasing bright red shade. The dyeing is similar in shade and light fastness but superior in fastness lTIHa to perspiration, washing and fulling'as compared to 'th'e corresponding dye containing an acetyl amino-"group.

The2-sulfo-4-chloroacetylamino aniline is prepared by the slow' addition of a little more than one'e'quiVaIent of chloroacetylchloride to an alkaline solution-oi one equivalent of 'sulfo p- 'phenylene diamine at 20-30 C. The chloroaddition of acid or it may be 'diazjotized directly acetylaminocompound may be isolated'by the BrCHzC O-NH It is similar in shade and properties to the dye described in Example 1. The 2-sulfo-4 bforno acetylaminoaniline is prepared from bromoacetyl bromide in a manner similar to that given in Example 1 for the preparation of the chloro compound.

s Example 3 when z suiio-s ehiereseety emnio aniline is used in place or the para-nomaiii'Eiiafiiple'l,

a red dye is obtained which "is represented by the formula clcnic O-NH It is 'yelibwer in shadehut otherwise similar in properties to the dye or Example 1'.

ne less component s" pr pared b? treatment or smio-m-pne yiene-aiainine with su'mcient chioroaeetm amends so that therea tioh anxtiire no longer eoupies witha test solution or a dress component, showing tfi 'afinno group. which is pars to the somatic and grou is entirely converted to the chloroac'etylalrii'fio group.

Example 4 A s'blution of 482 parts of the dye represented by the formula SOzNa (which'can be prepared by known procedures by coupling p-nitro-ani1ine-o-su1ionic acid diazo with 2-amino-G-sulfo-B-naphthol in an acid medium followed by making alkaline and reducingthe nitro group with sodium sulfhydrate) in 8000- parts of water at 25 C is treated-gradually with 113 parts of chloroacetyl chloride (or with a solution of the latter in carbon tetrachloride). The reaction mixture is maintained slightly alkaline to Brilliant Yellow solution by the addition from time to time of sodium carbonate solution. More chloroacetyl chloride is added,;if an acidified test portion of the reaction mixture gives a blue coloration with sodium nitrite solution. When u the reaction is completes test sample upon the addition ofacid and sodium nitrite does not give a blue color," showing that-the; amino group para to the azo linkage is completely converted to the chloroacetylamino product.

The dye is salted and isolated by filtration. It is represented by the formula 0101170 0-NH N=N SbaH H0 When an appropriate amount of chloroacetic anhydride in carbon tetrachloride is used in place of the chloroacetyl chloride of Example 4, a dye substantially identical in properties with the dye described in Example 4 is obtained.

' Example 6 A When an appropriate amount of bromoacetyl bromide in carbon tetrachloride is used in place of the chloracetyl chloridein Example 4', a dye is obtained which corresponds in properties to those ofthe dye described Example 2.

Eztdmble 7 When an appropriate amount of 2-bromopropionyl'b-romide, in carbon tetrachloride solution, is used in plac'eof the-chloracetyl chloride in Example 4, a dye is obtained which is repre sentd by the formula dyeings on wool which are similarin light fastnose to the known dyes but with good wet fastness which is not possessed by the light fast red dyes of the prior art.

From the foregoing disclosure it will be reco nized that the invention is susceptible of modifiform by the formula NEN soin H0 SOrH wherein a is (on o! a you, common by 5. m red when dye root-mm by the dragon and methyl, X is one o! a group oonsisti z iormuli of chlorine and bromine, the group NH! 0-1pm;- no: so NH N N t is in the 4 or 5 position with'relerence to the am group and the 80:11 group of the diam no 7 component is in the 2-position with reference to the azo group. th e 10 2. A red monazo dye in accordance wi claim 1 1 m which the group RF-cnx-co-nmis' m the f fi Y mm by, the 4-position with reference to the axe group. om t 3. The red monezo dye in accordance with I claim 1 in which X is chlorine.

4. The red dye represented by the formula I soon .30

mcmco-Nn N=N 7 50m om no i DONOVAN IE. KVALNES.

' OIB 

